Grease manufacture

ABSTRACT

In a process for manufacturing a calcium complex grease in which there is incorporated an ethylene-vinyl esterorganic acid terpolymer as an improving agent, a method is provided for improving grease formulation, obtaining improved yield and making use of previously unsuitable oils by introducing the terpolymer to the charge of the lubricating vehicle and thickening agent components prior to saponification.

United States Patent [19 Sayles Sept. 9, 1975 GREASE MANUFACTURE [75]inventor: Francis S. Sayles, Rocky Hill, NJ. Primary Examnfer DelbeflGamz Asszstanl Exammerl. Vaughn [7 As g'n l M il Oil Corporation, NewYork, Attorney, Agent, or Firm-Charles A Huggett; Oswald NY. G. Hayes[22] Filed: July 1, 1974 [21 1 App]. No.: 484,909 [57] ABSTRACT In aprocess for manufacturing a calcium complex [52] US Cl 252/36; 252/40.5;252/5 l .5 R; grease in which there is incorporated an ethylene-vinyl252/5l.5 A; 252/56 R esterorganic acid terpolymer as an improving agent,a [5] Int. Cl. ClOm 5/16; ClO 5/12 method is provided for improvinggrease formulation, [58] Field of Search 252/36, 5 l .5 R, 51.5 A,obtaining improved yield and making use of previously 252/56 R, 40.5unsuitable oils by introducing the terpolymer to the charge of thelubricating vehicle and thickening agent [5 6] References Citedcomponents prior to saponification.

UNITED STATES PATENTS 15 Claims, N0 Drawings 3,705,853 12/1972 Fran etal. 252/36 GREASE MANUFACTURE BACKGROUND OF THE INVENTION 1. Field ofthe Invention This invention relates to grease manufacture and, in oneof its aspects, relates more particularly to a process for manufacturinga calcium complex grease in which there is incorporated in theformulation an ethylenevinyl ester-organic acid terpolymer for improvingwater wash-out resistance and resistance to softening at relatively hightemperature environments.

2. Description of the Prior Art In commonly assigned US. Pat. No.3,705,853, issued Dec. 12, 1972, there are provided grease compositionshaving improved resistance to water wash-out and resistance to softeningat high temperature conditions, comprising calcium complex greasescontaining ethylene-vinyl ester organic acid terpolymers as improvingagents. More specifically, the terpolymers of these formulations have amelt index of 0.5 to 200 and contain: l at least 65 percent, by weight,of ethylene, (2) at least 5 percent, by weight, of a secondethyleneically unsaturated monomer which is an ester of the groupconsisting of the vinyl esters of the lower (1-6 carbon) saturatedaliphatic carboxylic acids, the alkyl acrylates, the alkylmethacrylates, the dialkyl maleates and the dialkyl fumarates of thelower l6 carbon) aliphatic alcohols; and (3) 0.01 to 3 percent, byweight, of a third ethylenically unsaturated monomer of the groupconsisting of acrylic, methacrylic, itaconic, maleic and fumaric acids;the anhydrides of itaconic, maleic and fumaric acids; the alkyl hydrogenmaleates and the alkyl hydrogen fumarates; the monoacrylates andmonomethylacrylates of glycols', 2-hydroxy-3-aminopropyl allyl ether,allyl glycerol ether, divinyl glycol, Z-dimethylaminoethyl acrylate,Z-dimethylaminoethyl methacrylate and N-vinyl pyrrolidone. Thepreparation of the above-described terpolymer improving agents is morefully disclosed in U.S. Pat. No. 3,2l5,657, issued Nov. 2, 1965.

The thickening agents employed in the greases of the present inventioncomprise calcium complex soaps, including calcium acetate complex soapsand calcium lead acetate complex soaps.

Oils used in the greases of this invention can be min eral or syntheticoils of lubricating viscosity. Suitable mineral oils have a viscosity(SUS) of at least 40 seconds at 100F, and particularly those within therange of about 60 seconds to about 6,000 seconds at 100F.

Synthetic vehicles can be used, instead of mineral oils, or incombination therewith. Typical synthetic vehicles are: polypropylene,polypropylene glycol, trimethylol propane esters, neopentyl andpentacrythritol esters, di(2-ethyl hexyl) sebacate, di-(2-ethyl hexyl)adipate, dibutyl phthalate, polyethylene glycol di(2- atoms per moleculein the presence of an aliphatic halide and a Zielger-type catalyst.

With reference to the terpolymer improving agents of the presentinvention, preferred terpolymers contain from about 20 to about 30percent, by weight, of the aforementioned group (2) component, i.e. thesecond ethylenically unsaturated monomer component; and from about 0.1to about 1 percent, by weight, of the aforementioned group (3)component, i.e. the third ethylenically unsaturated monomer component.Representative preferred terpolymers comprise, in addition to ethylene,from about 20 to about 30 percent, by weight, vinyl acetate and fromabout 0.1 to about 1 percent, by weight, acrylic acid; from about 20 toabout 30 percent, by weight, vinyl acetate and from about 0.1 to aboutl%, by weight, methacrylic acid; from about 20 to about 30 percent, byweight, ethyl acrylate and from about 0.1 to about 1 percent, by weight,acrylic acid; from about 20 to about 30 percent, by weight, ethylacrylate and from about 0. l to about 1 percent, by weight methacrylicacid; from about 20 to about 30 percent by weight, methyl methacrylate,and from about 0.1 to about 1 percent, by weight, acrylic acid; and fromabout 20 to about 30 percent, by weight, methyl methacrylate and fromabout 0.l to about 1 percent, by weight, methacrylic acid.

Insofar as the quantity of terpolymer improving agent is concerned, thelatter as previously indicated, is employed in a minor amount sufficientto incorporate in the grease formulation the desired resistance to Waterwash-out and resistance to softening at high temperature conditions.Particularly preferred are greases in which the terpolymer is present inan amount of at least about 0.01 percent, by weight, and for mostpurposes, the presence of the terpolymer in an amount from about 0.] toabout 5 percent, by weight, produces highly satisfactory improved greasecompositions.

In preferred modifications, the terpolymer contains from about 20 toabout 30 percent, by weight, of the group (2) monomer component and fromabout 0.1 to about 1 percent, by weight, of the group (3) monomercomponent. A particularly preferred terpolymer is one having a meltindex of about 6 and containing about 71.8 percent, by weight, ethylene,about 25 percent, by weight, vinyl acetate and about 0.7 percent, byweight, methacrylic acid.

In accordance with the procedure set forth in the aforementioned U.S.Pat. No. 3,705,853, the abovedescribed greases are prepared byconventional grease manufacturing procedures which are well known tothose skilled in the art. In such conventional procedures, it hasheretofore been the practice to introduce the vehicle and thickeningagent components into the mixing vessel or contactor. Aftersaponification and an ultimate grease formulation has been achieved, inaccordance with usual procedure, the aforementioned terpolymer is addedto the finished grease to achieve the ultimate desired product. Infollowing such procedure, however, it has been found that completedispersion of the terpolymer is a calcium complex soap grease (includingcalcium acetate complex grease and calcium lead-acetate complex grease)is not achieved and, in many instances, a satisfactory yield is notobtained.

SUMMARY OF THE INVENTION In accordance with the present invention, ithas now been found that a more complete dispersion of the aforementionedterpolymer, improved yields are ob tained and use of hiterto unsuitableoils are able to be incorporated in calcium complex greases byintroducing the terpolymer in the charge of lubricating vehicle andthickening agent components prior to saponifi- 5 cation. Those skilledin the art have long recognized the influence of oils in varioussoap-base systems in that calcium acetate complex and calcium leadacetate complex grease bases are affected, for example, by substitutinga paraffin oil for a naphthenic base oil. Naphthenic base oils notablyresult in a firm-bodied soap base, thereby resulting in good yield.Paraffin oils, on the other hand, in the same soap base, yieldsoft-bodied bases resulting in relatively poor yields.

DESCRIPTION OF SPECIFIC EMBODIMENTS In order to demonstrate theimprovement realized in obtaining more complete dispersion of theaforementioned terpolymers, improvement in yield, and use of hithertounsuitable oils are able to be incorporated in calcium complex greasesby introducing the terpolymer to the charge of lubricating vehicle andthickening agent components prior to saponification, comparative datawere obtained, as shown in the examles of the following Tables I and II.The grease-making technique employed in the examples ofTables I and II,in general, involves charging a contactor with appropriate amounts offatty saponifable material, lime, litharge, water and base oil Aftersaponification, the soap base is discharged to a finishing kettle. Insome examples the terpolymer was added at this point, in other examplesit constituted a part of the orginal charge to the contactor. In theformer cases dehydration of the soap base is concurrent with dispersionof the terpolymer therein. Cooling, addition of various additivepackages, homoginization and final addition of oil, complete themanufacture. The terpolymer employed in the examples of Tables I and IIhad a melt index of about 6 and contained about 71.8 percent, by weight,ethylene, about percent, by weight, vinyl acetate and about 0.71percent, by weight, methacrylic acid. The base oils employed in theexamples of Table I comprised either a 500 SUS solvent naphthenicneutral oil, with a V.l. of 60 or 300 SUS solvent paraffinic neutral oilhaving a VI. of 90. The base oils employed in the examples of Table IIcomprised either a 900 SUS solvent naphthenic neutral oil having a V.I.of 65 or a 300 SUS solvent paraffinic neutral oil having a \/.l. of 90.

INFLUENCE OF TERPOLYMER OF YIELD (Z FATTY MATERIAL) AND BASE OII. ON THEMANUFACTURE OF CALCIUM-LEAD ACETATE COMPLEX AND CALCIUM ACETATE COMPLEXGREASES TABLE I CALCIUM-LEAD ACETATE COMPLEX GREASES Ter- Fatty polymerAdded Material Base Oil Consistency Ex. Present To '75 Type UW/W l I NoW 12.0 Naphthenic 3 l9/328 2 Yes Finishing I21) Naphthenic 267/298Kettle 3 Yes Contactor 10.5 Naphthcnic 280/301 Charge 4 No I50Paraffinic 365/378 5 Yes Finishing I50 Paraffinic 347/36l Kettle 6 YesContactor l l.U Paraffinic 277/295 Charge INFLUENCE OF TERPOLYMER OFYIELD FATTY MATERIAL) AND BASE OIL ON THE MANUFACTURE OF CALCIUM-LEADACETATE COMPLEX AND CALCIUM ACETATE COMPLEX GREASES l J UW/WUnworked/btl Stroke Worked, ASTM D-2 l7 As will be apparent from thecomparative examples of Tables I and II, significantly higher amounts offatty material or softer consistency results are encountered in thefinished grease where the terpolymer is either absent, (Examples I and 4in each table), or introduced into the finished grease (Examples 2 and 5in each table,) contrasted with the presence of significantly smalleramounts of fatty material or firmer consistency results when theterpolymer is introduced in the charge to the contactor (Examples 3 and6 in each table).

While this invention has been described with reference to preferredcompositions and components therefor, it will be understood by thoseskilled in the art that departure from the preferred embodiments can beeffectively made and are within the scope of the specification.

I claim:

1. In a process for manufacturing a calcium complex grease in whichthere is incorporated an ethylene-vinyl ester-organic acid terpolymer asan improving agent, the method for improving grease formation whichcomprises introducing said terpolymer to the charge of lubricatingvehicle and thickening agent components prior to saponification.

2. A process, as defined in claim 1, wherein the vehicle of said greasecomprises a paraffinic mineral lubricating oil.

3. A process, as defined in claim I, wherein the vehicle of said greasecomprises a synthetic lubricating oil.

4. A process, as defined in claim 1, wherin said terpolymer is presentin said grease in an amount of at least 0.0l%, by weight.

5. A process, as defined in claim I, wherein said terpolymer is presentin said grease in an amount from about 0.1 to about 5 percent, byweight.

6. A process, as defined in claim 1, wherein said grease compositioncomprises a lubricating vehicle, a grease-forming quantity of athickening agent and a minor effective amount of an improving agentcomprising a terpolymer having a melt index of 0.5 to 200 andcontaining: l at least 65 percent, by weight, of ethylene, (2) at least5 percent, by weight, of a second ethylenically unsaturated monomerwhich is an ester of the group consisting of: the vinyl esters ofsaturated aliphatic carboxylic acids having l6 carbons; the alkylacrylatcs, the alkyl methacrylates, the dialkyl maleates and the dialkylfumarates of aliphatic alchols having 1-6 carbons; and (3) 0.0l to 3percent, by weight of a third ethylenically unsaturated monomer of thegroup consisting of: acrylic, methacrylic, itaconic, maleic and fumaricacids: the anhydrides of itaconic, maleic and fumaric acids; the alkylhydrogen maleates and the alkyl hydrogen fumarates', the monoacrylatesand monomethyacrylates of glycols; 2-hydroxy-3- aminopropy] allyl ether,allyl glycerol ether, divinyl glycol, Z-dimethylaminomethyl acrylate, 2-dimethylaminoethyl methacrylate and N-vinyl pyrrolidone.

7. A process, as defined in claim 6, wherein said terpolymer containsfrom about to about percent, by weight of the group (2) monomercomponent.

8. A process, as defined in claim 6, wherein the terpolymer containsfrom about 20 to about 30 percent, by weight, of the group (2) componentand from about 0.1 to about 1 percent, by weight, of the group (3)monomer component.

9. A process, as defined in claim 6, wherein the terpolymer containsfrom about 20 to about 30 percent, by weight, of vinyl acetate and from0.1 to about 1 percent, by weight, acrylic acid.

10. A process, as defined in claim 6, wherein the terpolymer containsfrom about 20 to about 30 percent, by weight, vinyl acetate and fromabout U. l to about 1 percent, by weight, methacrylic acid.

11. A process, as defined in claim 6, wherein the terpolymer containsfrom about 20 to about 30 percent, by weight, ethylacrylate and fromabout 0.1 to about 1 percent, by weight, acrylic acid.

12. A process, as defined in claim 6, wherein the terpolymer containsfrom about 20 to about 30 percent, by weight, ethylacrylate and fromabout 0. l to about 1 percent, by weight, methacrylic acid.

13. A process, as defined in claim 1, wherein the terpolymer containsfrom about 20 to about 30 percent, by weight, methylmethacrylate andfrom about 0.1 to about 1 percent, by weight, acrylic acid.

14. A process, as defined in claim 6, wherein the terpolymer containsfrom about 20 to about 30 percent, by weight, methylmethacrylate andfrom about 0.1 to about 1 percent, by weight, mcthacrylic acid.

15. A process, as defined in claim 6, wherein the terpolymer has a meltindex of about 6 and contains about 7.18 percent, by weight, ethylene,about 25.0 percent, by weight, vinyl acetate and about 0.7 percent, by

weight, methacrylic acid.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTIONPATENT NO. 3,904,534

DATED September 9, 1975 |NVENTOR(S) I FRANCIS S. SAYLES It is certifiedthat error appears in the ab0ve-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 6, line 22, "7.18" should read -7l.8-

Signed and Scaled this Attest:

RUTH C. MASON C. MARSHALL DANN Alresnng Officer Commissioner of Patentsand Trademarks

1. IN A PROCESS FOR MANUFACTURING A CALCIUM COMPLEX GREASE IN WHICHTHERE IS INCORPORATED AN ETHYLENE-VINYL ESTER-ORGANIC ACID TERPOLYMER ASAN IMPROVING AGENT, THE METHOD FOR IMPROVING GREASE FORMATION WHICHCOMPRISES INTRODUCING SAID TERPOLYMER TO THE CHARGE OF LUBRICATINGVECHILE AND THICKENING AGENT COMPONENTS PRIOR TO SAPONIFICATION.
 2. Aprocess, as defined in claim 1, wherein the vehicle of said greasecomprises a paraffinic mineral lubricating oil.
 3. A process, as definedin claim 1, wherein the vehicle of said grease comprises a syntheticlubricating oil.
 4. A process, as defined in claim 1, wherin saidterpolymer is present in said grease in an amount of at least 0.01%, byweight.
 5. A process, as defined in claim 1, wherein said terpolymer ispresent in said grease in an amount from about 0.1 to about 5 percent,by weight.
 6. A process, as defined in claim 1, wherein said greasecomposition comprises a lubricating vehicle, a grease-forming quantityof a thickening agent and a minor effective amount of an improving agentcomprising a terpolymer having a melt index of 0.5 to 200 andcontaining: (1) at least 65 percent, by weight, of ethylene, (2) atleast 5 percent, by weight, of a second ethylenically unsaturatedmonomer which is an ester of the group consisting of: the vinyl estersof saturated aliphatic carboxylic acids having 1-6 carbons; the alkylacrylates, the alkyl methacrylates, the dialkyl maleates and the dialkylfumarates of aliphatic alchols having 1-6 carbons; and (3) 0.01 to 3percent, by weight of a third ethylenically unsaturated monomer of thegroup consisting of: acrylic, methacrylic, itaconic, maleic and fumaricacids: the anhydrides of itaconic, maleic and fumaric acids; the alkylhydrogen maleates and the alkyl hydrogen fumarates; the monoacrylatesand monomethyacrylates of glycols; 2-hydroxy-3-aminopropyl allyl ether,allyl glycerol ether, divinyl glycol, 2-dimethylaminomethyl acrylate,2-dimethylaminoethyl methacrylate and N-vinyl pyrrolidone.
 7. A process,as defined in claim 6, wherein said terpolymer contains from about 20 toabout 30 percent, by weight of the group (2) monomer component.
 8. Aprocess, as defined in claim 6, wherein the terpolymer contains fromabout 20 to about 30 percent, by weight, of the group (2) component andfrom about 0.1 to about 1 percent, by weight, of the group (3) monomercomponent.
 9. A process, as defined in claim 6, wherein the terpolymercontains from about 20 to about 30 percent, by weight, of vinyl acetateand from 0.1 to about 1 percent, by weight, acrylic acid.
 10. A process,as defined in claim 6, wherein the terpolymer contains from about 20 toabout 30 percent, by weight, vinyl acetate and from about 0.1 to about 1percent, by weight, methacrylic acid.
 11. A process, as defined in claim6, wherein the terpolymer contains from about 20 to about 30 percent, byweight, ethylacrylate and from about 0.1 to about 1 percent, by weight,acrylic acid.
 12. A process, as defined in claim 6, wherein theterpolymer contains from about 20 to about 30 percent, by weight,ethylacrylate and from about 0.1 to about 1 percent, by weight,methacrylic acid.
 13. A process, as defined in claim 1, wherein theterpolymer contains from about 20 to about 30 percent, by weight,methylmethacrylate and from about 0.1 to about 1 percent, by weight,acrylic acid.
 14. A process, as defined in claim 6, wherein theterpolymer contains from about 20 to about 30 percent, by weight,methylmethacrylate and from about 0.1 to about 1 percent, by weight,methacrylic acid.
 15. A process, as defined in claim 6, wherein theterpolymer has a melt index of about 6 and contains about 7.18 percent,by weight, ethylene, about 25.0 percent, by weight, vinyl acetate andabout 0.7 percent, by weight, methacrylic acid.